Process for improving the dyeing of living human hair with anionic direct dyes



United States Patent M 3,464,778 PROCESS FOR IMPROVING THE DYEING OF LIVING HUMAN HAIR WITH ANIONIC DI- RECT DYES Peter Berth, Dusseldorf-Benrath, Giinter Reese, Dusseldorf, and Karl-Josef Boosen, Dusseldorf-Holthausen, Germany, assignors to Therachemie chemisch therapeutische Gesellschaft m.b.H., Dusseldorf, Germany No Drawing. Filed Aug. 26, 1965, Ser. No. 482,923 Claims priority, application Germany, Sept. 2, 1964, T 26,923 Int. Cl. A61k 7/12; D06p 1/68; C09b 67/00 U.S. Cl. 8-101 18 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a process for improving the dyeing of living human hair with anionic direct dyestuffs. The compounds which cause the improvement are ketones having to carbon atoms, esters of aliphatic alcohols (1 to 8 carbon atoms) and saturated carboxylic acids (2 to 8 carbon atoms); pyridine derivatives; carbonic and sulfurous acid esters of alkylene glycols (2 to 4 carbon atoms); dithiohydantoin; tetrahydrothiophene dioxide; thionaphthene and piperazine hydrate.

The invention relates to boosters for anionic direct dyestuffs which facilitate the dyeing of hair, more particularly human hair, and to a process for their application.

For the dyeing of hair so-called oxidation dyes are employed at a large scale, such as aromatic diamines, aminophenols or polyhydroxy compounds. However, direct dyes also have been used which have the advantage not to require the addition of oxidizers upon application. It is known from the textile industry that dyeing and the qualities of the coloring obtained thereb can frequently be improved by means of particularly high or low pH values, elevated temperatures or extensions of the time of application. Upon dyeing of hair, and particularly living human hair, such methods evidently cannot be em ployed. Moreover, it often is necessary to apply entirely new dyes as agents for dyeing of human hair, and this is especially true for direct dyes.

It also has been attempted to improve the usefulness especially of such dyes of limited solubility, by the addition of materials as butanol, benzyl alcohol or addition products of phenols or alcohols on ethylene oxide. However, it has been found that success has been limited to very few instances.

It is the object of the invention to present agents and a process for their application which facilitate ready dyeing of hair, particularly living human hair, with anionic direct dyestuffs, i.e., to improve the quality of the color, its intensity and resistance to rubbing and abrasion. All this is attained, according to the invention, by treating the hair with solutions, dispersions or emulsions of compounds of the following series:

(a) ketones having 5 to 10 carbon atoms;

(b) esters of aliphatic alcohols having 1 to 8 carbon atoms with saturated carboxylic acids having 2 to 8 carbon atoms;

(c) pyridine derivatives;

(d) carbonic and sulfurous acid esters of alkyleneglycols having 2 to 4 carbon atoms;

(e) dithiohydantoin, tetrahydrothiophene dioxide, thionaphthene, piperazine hydrate.

Treatment of the hair can be carried out by rinsing it with a solution or emulsion containing one or more of the compounds named above, followed by dyeing with the direct dyes in the conventional manner. However, it is equally feasible to wash the hair first and to add the booster agents to the last rinse directly. The concentration of the agents ranges from 0.1 to 10 weight percent, preferably l to 5 percent. The temperatures are 15 to 40 C., preferably room temperature.

If desired, this treatment furthermore can be combined with the actual dyeing by incorporating the compounds named in the dyeing preparation, either during the production of the latter or else shortly before its application to the hair. Concentrations and temperatures are the same as named above.

The advantages of this novel process are found in the fact that frequently the quantity of dyestuffs to be applied can materially be reduced without sacrificing the intensity of the dye. It also is feasible in many instances to increase the color intensity considerably with the process according to the invention when initially a rather weak coloration is present.

A further advantage is the increase in the resistance to abrasion and rubbing with simultaneous improvement of the dyeing process.

The single elfects depend, to a certain extent, on the booster used and on the characteristics of the dyestutf itself, but it has been established that the improvements named have been attained in all instances. For practical application, the compounds named below are particularly interesting from a technological and economical point of view. They are special representatives of (a)(c) above, but are not presented to be a limitation:

(a) cyclohexanone, 2-propylcyclohexanone, p-methoxyacetophenone, p-hydroxyacetophenone, p-aminoacetophenone;

(b) propylacetate, octylacetate, ethylbenzoate, p-nitrobenzoic acid methylester, diethylmalonate, dimethyladipate, diethylphthalate;

(c) pyridine-Z-carbinol, pyridine-Z-thiocarbinol, pyridine- 3-carbinol, pyridine-Z-ethanol, pyridine-3-aldehydethiosemicarbazone, picolinic acid, dipicolinic acid, nicotinic acid, picolinic acid-n-butylester, picolinic acid-N-oxide, 2- and 3-pyridyloxymethanesulfonic acid, 2-picolylamine, 2,2'-pyridil, 2,2'-pyridoin, pyridinium-(pyridinium-N-acetate)chloride, pyridine-Z-aldehyde, pyridine- 2-aldoxime, pyridyl-3-acrylic acid, 2-cyanopyridine, 2- picolylmethylamine, piperidine.

If desired, mixtures of these compounds can be used, especially mixtures of compounds of the same group. It goes without saying that the mutual chemical compatibility and that with other possibly present materials must be considered.

The pH value of the solutions containing these boosters can be adapted to a large measure to the prevailing requirements and desires. Good results have been obtained with preparing solutions and/or last rinses which were not alkaline, but acid or neutral.

Suitable anionic direct dyes are those known per se for the purpose at hand, particularly those based on acidic azo dyes and triarylmethane dyes as well as corresponding anthraquinone or aminoanthraquinone dyes.

The dyes are applied in the conventional concentrations of 0.1 to 5 weight percent, and preferably 0.5 to 3 percent. If, however, the effect of an increased color intensity is not desired, the commonly employed quantities can greatly be decreased, in some instances down to approximately M of the usual amount, with the process according to the invention.

The invention now will be further illustrated by the following examples. However, it should be understood that these are given merely by way of explanation, and not of limitation, and that numerous changes may be made in the details without departing from the spirit and the scope of the invention as hereinafter claimed.

Example 1 Naturally greyed living human hair was dyed with a solution containing 1 weight percent of an anionic direct dye of the Formula 1 Example 2 Naturally grey hair was shampooed, and the last rinse after shampooing was carried out with a 2 weight percent aqueous solution of weight percent pyridine-Z-thiocarbinol.

The hair then was dyed with a cream containing 1 weight percent of an anionic direct dye having the Formula 2 The pH of the cream was 7, and the time of action on the hair 20 minutes at room temperature. A good reclpurple color was obtained whose intensity was copsiderably stronger than that which resulted from like treatment but without the rinse with the pyridine-Z-thiocarbinol solution.

Example 3 Grey hair was dyed a weak yellow within 20 minutes at room temperature with a 0.1 weight percent aqueous solution of a dyestulf having Formula 3 a) OH The color of the hair thus dyed became a rich canary yellow when, at otherwise like conditions, a dyeing liquid was employed which additionally contained 2 weight percent of either diethyloxolate or pyridine-Z-aldoxime.

Example 4 Grey hair was dyed for 20 minutes at room temperature with an aqueous solution containing 1 Weight percent of a dyestuff having Formula 4 B r C// B r C O O H and thereby assumed a weak red color.

The color of the hair became a brilliant red when the dyeing solution simultaneously contained 3 weight percent ethyleneglycol sulfite.

4 Aqueous solutions were produced containing as anionic dyestulf 1 weight percent of a material having Formula 5 The dyes furthermore contained one of the booster materials named in Table 1 in the quantities listed therein. The solutions were adjusted to a pH of 9.5 with aqueous ammonia. For dyeing of living grey human hair, these solutions were applied at room temperature for 20 minutes. This was followed by shampooing and drying. in all instances, considerable improvement was obtained over the weak red color which the hair assumed in a like procedure but under omission of the booster substance from the solution.

In Table 2, other dyes and their Color Index Numbers are listed which can be substituted for that named as Formula 5, and corresponding results obtained.

TABLE 1 N 0. Material Wt. percent 1 Cyclohexanone 4 2 p-Metlloxyacetophonone 3 3 pHydroxyacetophenone 6 4 p-Aminoacetophenone... 5 5-. n-Propylacetate 3 6 Diethylmalonate 3 7 r- Diethylphthalate 5 8 Pyridine-Zaldehyde... 2 9.- Pyridine-laldoximan 2 10 Pyridine-Bacrylie acid 2 11 2-cyanopyridine 2 12 2-picolylmethylamme 2 13 Piperidine 2 14 Dithiohydantoin 3 15- Tetrahydrothiophene dioxide 2 16 Thionaphthene 4 17- Ethyleneglyeol sulfit-e 5 l8 1,2-propyleneglycol sultit 5 19. Ethyleneglyeol carbonate 10 20 Piperazine hydrate 5 21 'i-mercaptopyridine 5 TABLE 2 Dyestuff: Color Index No. Naphthol Yellow S 10316 Metanil Yellow Extra 13065 Acilancorcein MOO 27290 Acilan Black 10 B 20470 Chrysoin S 14270 Eosin G Conc. 45380 Acilan Green BS 44090 Uranin A extra conc. 45350 Alizarin Direct Blue AGG 62125 Dyes named in Belgian Patent 652,619

What is claimed is:

1. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solu tions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 Weight percent of a member selected from the group consisting of cyclohexanone, 2-propyl-cyclohexanone, pmethoxyacetophenone, p-hydroxyacetophenone, p-aminoacetophenone and mixtures thereof.

2. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of a member selected from the group consisting of pyridine-Z-carbinol, pyridine-Z-thiocarbinol, pyridine-S-carbinol, pyridine-Z-ethanol, pyridine 3 aldehyde-thiosemicarbazone, picolinic acid, dipicolinic acid, niootinic acid and picolinic acid-n-butylester, picolinic acid- N-oxide, 2- and 3-pyridyloxymethane-sulfonic acid, 2-picolylamine, 2,2'-pyridil, 2,2-pyridoin, pyridinium-(pyridinium-N-acetate)-chloride, pyridine-Z-aldehyde, pyridine- 2-aldoxime, pyridyl-3-acrylic acid, Z-cyanopyridine, 2-picolyl-methylamine, piperidine and mixtures thereof.

3. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquid containing substantially 0.5 to weight percent of carbonic and sulfurous acid esters of alkylene glycols having 2 to 4 carbon atoms or mixtures thereof.

4. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially to 40 C., said liquids containing substantially 0.5 to 10 weight percent of a member selected from the group consisting of dithiohydantoin, tetrahydrothiophene dioxide, thionaphthene, piperazine hydrate and mixtures thereof.

5. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C. said liquids containing substantially 0.5 to 10 weight percent of ethylbenzoate.

6. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of p-nitrobenzoic acid methyl ester.

7. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of diethylmalonate.

8. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C. said liquids containing substantially 0.5 to 10 weight percent of dimethyladipate.

9. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of diethylphthalate.

10. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair prior to the application of said dye With a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 Weight percent of a member selected from the group consisting of cyclohexanone, Z-propyl-cyclohexanone, pmethoxy-acetophenone, p-hydroxyacetophenone, p-amino acetophenone and mixtures thereof.

11. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of a member selected from the group consisting of pyridine-Z-carbinol, pyridine-Z-thiocarbinol, pyridine-3-carbinol, pyridine-Z-ethanol, pyridine-3-aldehyde-thioserni carbazone, picolinic acid, dipicolinic acid, nicotinic acid, and picolinic acid-n-butylester, picolinic acid-N-oxide, 2- and 3-pyridyloxymethane-sulfonic acid, 2-picolylamine, 2,2-pyridyl, 2,2-pyridoin, pyridinium-(pyridinium-N-ace tate)-chloride, pyridine-Z-aldehyde, pyridine-Z-aldoximide, pyridyl-3-acrylic acid, 2-cyano-pyridine, 2-picolyl-methylamide, piperidine and mixtures thereof.

12. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of carbonic and sulfurous acid esters of alkylene glycols having 2 to 4 carbon atoms or mixtures thereof.

13. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of a member selected from the group consisting of dithiohydantoin, tetrahydrothiophene dioxide, thionaphthene, piperazine hydrate and mixtures thereof.

14. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solution and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 Weight percent of ethylbenzoate.

15. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of p-nitrobenzoic acid methyl ester.

16. A method of boosting the action of anionic direct dye on human hair Which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 1540 C., said liquids containing substantially 0.5-10 weight percent of diethylmalonate.

17. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 1540 C., said liquids containing substantially 0.5-1O weight percent of dimethyladipate.

18. A method of boosting the action of anionic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of diethylphthalate.

References Cited UNITED STATES PATENTS 2,069,215 2/1937 Chambers 885 X 2,585,610 2/1952 WittWer 8--10 FOREIGN PATENTS 239,365 7/ 1962 Australia.

ALBERT T. MEYERS, Primary Examiner VERA C. CLARKE, Assistant Examiner US. Cl. X.R. 

